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Sodium naphthenates (NaNs), found in crude oils and oil sands process-affected water (OSPW), can act as surfactants and stabilize undesirable foams and emulsions. Despite the critical impact of soap-like NaNs on the formation, properties, and stability of petroleum and OSPW foams, there is a significant lack of studies that characterize foam film drainage, motivating this study. Here, we contrast the drainage of aqueous foam films formulated with NaN with foams containing sodium dodecyl sulfate (SDS), a well-studied surfactant system, in the relatively low concentration regime ( c /CMC < 12.5). The foam films exhibit drainage via stratification, displaying step-wise thinning and coexisting thick–thin regions manifested as distinct shades of gray in reflected light microscopy due to thickness-dependent interference intensity. Using IDIOM (interferometry digital imaging optical microscopy) protocols that we developed, we analyze pixel-wise intensity to obtain thickness maps with high spatiotemporal resolution (thickness <1 nm, lateral ∼500 nm, time ∼10 ms). The analysis of interference intensity variations over time reveals that the aqueous foam films of both SDS and NaN possess an evolving, dynamic, and rich nanoscopic topography. The nanoscopic thickness transitions for stratifying SDS foam films are attributed to the role played by damped supramolecular oscillatory structural disjoining pressure contributed by the confinement-induced layering of spherical micelles. In comparison with SDS, we find smaller concentration-dependent step size and terminal film thickness values for NaN, implying weaker intermicellar interactions and oscillatory structural disjoining pressure with shorter decay length and periodicity. 

Ultrathin foam films containing supramolecular structures like micelles in bulk and adsorbed surfactant at the liquid–air interface undergo drainage via stratification. At a fixed surfactant concentration, the stepwise decrease in the average film thickness of a stratifying micellar film yields a characteristic step size that also describes the quantized thickness difference between coexisting thick–thin flat regions. Even though many published studies claim that step size equals intermicellar distance obtained using scattering from bulk solutions, we found no reports of a direct comparison between the two length scales. It is well established that step size is inversely proportional to the cubic root of surfactant concentration but cannot be estimated by adding micelle size to Debye length, as the latter is inversely proportional to the square root of surfactant concentration. In this contribution, we contrast the step size obtained from analysis of nanoscopic thickness variations and transitions in stratifying foam films using Interferometry Digital Imaging Optical Microscopy (IDIOM) protocols, that we developed, with the intermicellar distance obtained using small-angle X-ray scattering. We find that stratification driven by the confinement-induced layering of micelles within the liquid–air interfaces of a foam film provides a sensitive probe of non-DLVO (Derjaguin–Landau–Verwey–Overbeek) supramolecular oscillatory structural forces and micellar interactions.